Luminescence and excitation spectra in the region of the lowest-energy (3)MLCT electronic origins of the specifically deuterated complexes [Ru(bpy)(3-x)(bpy-6,6’-6(2))(x)](2+) (x = 0-3) in [Zn(bpy)(3)](ClO4)(2) and in the neat [Ru(bpy)(3-x)(bpy-6,6’-d(2))x](PF6)(2) (x = 0-3) crystals are reported. The deuteration of the 6,6’ positions represents a minimal variation of the bpy ligand. The x = 1, 2 systems show independent (3)MLCT transitions to the bpy-6,6’-d(2) and the bpy ligand. Intensity ratios of luminescence involving the bpy-6,6’-d(2) ligand or the bpy ligand in the x = 1, 2 systems vary as a function of temperature in accord with expectations. Measurements are made providing an estimate of similar to(2.1 +/- 0.8) x 10(9) s(-1) for the intramolecular 3MLCT excitation transfer from bpy-6,6’-d(2) to bpy. We also report a simple high-yield method to deuterate the 6,6’ positions of the bpy ligand.